Plastic similar to celluloid and manufacturing the same.



Winn se ies a v ARTHUR EICHENGRTTN, F BERLIN, GERMANY.

PLASTIC SIMILAR TO CELLULOID AND MANUFACTURING THE SAME Specification of Letters Patent.

Patented Jan. 16,1912.

No Drawing. Original application filed January 21, 1910, Serial No. 539,246. Divided and this application filed February 9, 1911.

To all whom it may concern:

Be itknown that I, ARTHUR EIcHEN- cRtiN, doctor of plnlosophy, chemist, a sub- Ject of the King of Prussia and the German Emperor, residing at 87 Konstanzerstrasse,

Berlin, Kingdompf Prussia, German Empire, have invented new and useful Im provements in Plastics Similar to Celluloid and lllanufacturing the Same, of which the following is a specification.

This invention relates to new plastics similar to cellu oid, and the manufacture of said plastics, and has for its object to obtain from cellulose acetates masses which are hard when cold and possess springy, elastic properties, while retaining the uninfiammable properties of the cellulose acetate.

I have foundthat cellulose acetates, particularly those soluble 'inacetone or acetic ether, can be readily converted into solutions, adapted to be worked up further into plastic masses, by the simultaneous action of alcohols and other liquids which do notdissolve cellulose acetates when heated and ture of hydrocarbons and alcohols under the action of heat. aliphatic have proved suitable, and of hydrocarbons the aromatic. Those boiling b elow-125 C. come particularly into consideration. The choice of the substances depends on the price. The formation of solutions of cellulose acetate in this manner I do not claim broadly herein, nor do I claim specifically the formation of liquid or fluent solutions, such being the matter of my copending application Serial No. 539,246,'filed January 21, 1910, whereof the present application is divisional.

In the process ofthe present embodimentof my invention, I treat the celluloseacetate which is to be dissolved with the mixture of hydrocarbon and alcohol and heat the same. It-is preferable to heat to approximatelythe boiling point of the solvent W1tl1 out exceeding the same.

When the solutions formed as just de- Of alcohols particularly the Serial No. 607,617.

this manner fluent solutions of cellulose acetate whichremain liquid or have-a syrupy character are obtained. Substances which are able to dissolve cellulose acetate act in like manner, such as dichlorhydrin, acetate of glycerin, ether of lactic acid, and so on. These additions have generally the property .of being non volatile at ordinary temperature and under ordinary storage conditions. The said additions have the effect of mak ing the masses soft. l/Vhen cold, honey-like viscous or gelatinizing masses are obtained according in each instance to the quantity of these admixtures. This is particularly the case when, as admixture, camphor or cam. phor substitutes, such as acidyl derivatives of primary and secondary aromatic amins, aromatic sulfo compounds, aromatic nitro compounds, or phenol derivatives are employed as admixture. However, when in proper proportions, the admixture of cellulose acetates, solvent and camphor substitute can be allowed to cool and congeal after solution has taken place to form firm, hard bodies which can be used for plastic purposes. Blocks are obtained which in spite of the presence of the entire solvent can be cut and readily worked up further. The

melted masses may be molded while still molten and only then allow to congeal. For example they may be allowed to pass through round orifices and in this manner I ofsolution as well as after the solution. So-

lutions thus obtained which are of such a character as to remain liquid on cooling may be applied on surfaces, such as paper, fabric, leather and the like. The solutions which congeal or solidify when cold may be poured hot on the supports or applied thereto .after congealing by pressure, for example by rollers or presses. In this case heat is preferably applied- My process can obtain plastics by treating the cellulose acetates in the presence ofrelativelysmall quantities of camphor or camphor substitutes with the mixture of non-solvents or non dissolving'liquids. With such compositions when the liquid has been'removed by evaporation from the firm elatinous mass which is first formed on coo a material is obtainedwhich is exactlyllke-celluloid with regard to elasticity and other properties.

In order to obtain masses from cellulose acetate having the properties of celluloid,'I 20 may treat cellulose acetate in alcohol and benzol with camphor or cam hor-substitutes under the-action of heat. en the solution cools firm, gelatinous masses are produced which can readily be worked up by 5 cutting, molding,.pressin and so on. The @solvent can be removed rom' these masses by evaporation, for example by passing over.

them dry air, by heating them, or the like.

For carrying my invention into practice it is not-necessary to com letely dissolve the cellulose acetate in the liquid mixture and finally to add the camphor substitutes. On the contra the camphor substitutes may be added during the process ,of solution. Also, cellulose acetates may be mixed with camphor or camphor substitutes and then treated with the solvent. The last process is preferable, particularly when it. is wished to employ as little liquid as possible.

In order to remove any impurities which maybe resent,'I may filter hot the solution of cellu o'se acetate made underv the action of'heat, leave it to cool and pour as an separated liquid from the cellulose acetate. The separated cellulose acetate still containing so vent is then mixed with camphor or camphor substitutes and exposed to pressure or heat or both; A very small quantity of camphor or camphor substitutes is requlred, as the cellulose acetates are in a very finely divided state orform.

Example I: 1 kg. cellulose acetate is dissolved in 2 k methyl alcohol and 1 k. toluol at 80 150 ms acetylmethylam- Im (so called mano and 100 ams epichlorhgdrm are. added to the soll ition and filtere hot. When cooling, the solutioncongeals to a firm mass which can readily be cut or pressed in molds or forced through shaped orifices. i

Examp le II: 1 kg. cellulose acetate is named with 240 grms. acetylmethylanilin dissolved in 900 grms. of a mixture of equal parts of alcohol and benzol, and vigorously kneaded for a long time at 30 to 40C. in

- herent mass. like cotton-wool.

by heat into the liquid state again, and

and benzol at 70 C. and filtered hot. After cooling, the entire .quantity of the cellulose acetate is precipitated in the form of a co- The same is separated from'the bulk of the liquid mixture and heated with 200 ms. trlchloranilin, when-a clear, celluloi '-like mass forms. If liquid mixtures which can act unfavor-" ablyon the celluloid-like masses, as e." g. a mixture of alcohol and water, be employed as solvent of the cellulose acetate, it is preferable to liberate the. cellulose acetate, which precipitates when .the mixture cools, from the liquid mixture still -contained"'35 therein and to moisten itlwith a suitable" mixture, such as alcohol-benzol.

The solutions obtained according to the 7 I herein described process can not only be-' worked up in the -manner of celluloid by allowing the same to dry in .the form of blocks and the likeand working up further" the firm masses thus obtained as in the vcase of celluloid, but the same may be converted these hot liquid solutlons can beworked up w 1 further by ejecting the same from correspondin orifices,-e. g. slits, when'the films congeal 1n the air and can be dried on suitable supports. Also, these hot liquid solutions can be cast in molds, o'r patterns may be dipped into the same whereupon the corresponding layers at once assume the corresponding shapes when coolin or the solutions may be poured from wide orifices directly on the smooth or impressed, possibly ornamented and molded supports, and allowed to congeal on these. Further, articles of all kinds can be coated with equal ease witlr a thick, celluloid-like layer by immersing them in .the' solutions, or. articles 'of greater length, such as wires, chains, threads, yarn, ropes, may be provided uniformly in one operation with a thick coating of cellulose acetate by passing them through the solutions. By admixing color- 7 ing matter with the solutions the masses. thus. obtaining can be colored optionally; also, for the purpose of obtaining special effects or properties other bodies, such as e. g. resins, mineral substances as white zinc, graphite, mica, asbestos or powdered metal,

and so on, may be added to them. This mode of treatment difi'ers entirely from that of celluloid in which the manufacture of highly concentrated solutions giving a glaze-like coating by a single a phcation or immersion has not been ossib e heretofore owin to the lack of a suitable solvent, and

in w ich it would be quite impossible to 130 work up the celluloid mass itself in the L matic hydrocarbon to act on cellulose ace-- tates in the presence of camphoror camphor substitutes in such proportions relative .to said acetate that homogeneous masses may be produced. I V

I 2., The process-of manufacturing solid cell'uloid like masses which comprises causing a heated mixture of an alcohol and an. aromatic hydrocarbon to act on cellulose acetates in the presence of camphor or camphor substitutes in such proportions relative to said acetate that homogeneousmasses may be produced, and evaporating the mixture of-alcohol and aromatic hydrocarbons.

luloid like masses which comprises causing a heated mixture of an alcohol and an aromatic 3. The maiiufacturing solid cel- I hydrocarbon to act on cellulose acetates in w the presence of non volatile solvents for eel-"- .l'ulose acetates and of camphor or camphor substitutes in such proportions relative to said acetate thathomogeneous masses may be produced.

LA celluloid-like plastic comprising cellulose acetate, an alcohol, an'aromatic hydro-- carbonand camphor or camphor substitutes.

5. A-celluloid-like plastic comprisingcelw, lulose acetate alcohol, toluol and camphor or camphor. substitutes.

' In test v ony whereof, I have signed my name-to thisspecification'in the presence of I ARTHUR EICHENGRUN. Witnesses: L HENRX HASPER,

Q W D MA'R HAU'PT two subscribing witnesses; 

